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Photocurable compositions containing group via aromatic onium salts

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US4058401A
US4058401A US05638982 US63898275A US4058401A US 4058401 A US4058401 A US 4058401A US 05638982 US05638982 US 05638982 US 63898275 A US63898275 A US 63898275A US 4058401 A US4058401 A US 4058401A
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epoxy
parts
salt
onium
resin
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James V. Crivello
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General Electric Co
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055Radiation sensitive composition or product or process of making
    • Y10S430/114Initiator containing

Abstract

Cationic polymerization of epoxy resin materials, such as epoxy monomers or prepolymers, can be achieved by use of certain radiation sensitive aromatic onium salts of Group VIa elements. Curable compositions are provided which can be used as sealants, coating compounds, encapsulants, etc.

Description

This is a continuation, of application Ser. No. 466,374, filed May 2, 1974 now abandoned.

CURABLE COMPOSITIONS

The present invention relates to epoxy resin compositions which can be cured by exposure to radiant energy.

Epoxy resins have generally been employed in a variety of applications requiring high performance materials. Cure of an epoxy resin can generally be achieved by two package systems based on the incorporation into the resin of active amine containing compounds or carboxylic acid anhydrides. These systems require thorough mixing of the ingredients; in addition, cure time can be several hours.

Another catalyst which can be used to cure epoxy resins as "one package" systems is based on the employment of a Lewis Acid catalyst in the form of an amine complex such as boron trifluoride-monoethyl amine. The Lewis Acid is released on heating; cure takes place within 1 to 8 hours and can require a temperature of 160° C and higher. As a result, these one package epoxy compositions cannot be employed to coat heat sensitive devices such as delicate electronic components. Nor can epoxy monomers having low boiling points be used due to the resulting losses to evaporation during cure.

As shown by Schlesinger, U.S. Pat. No. 3,703,296, certain photosensitive aromatic diazonium salts can be employed to cure epoxy resins. When photolyzed, these aromatic diazonium salts are capable of releasing, in situ, a Lewis Acid catalyst which can initiate the rapid polymerization of the epoxy resin. However, even though these one package epoxy resin mixtures can provide fast curing compositions, a stabilizer must be used to minimize cure in the dark during storage of these mixtures. Despite these measures, gellation of the mixture can occur even in the absence of light. In addition, nitrogen is released during UV-cure, which can result in film imperfections. Diazonium salts are generally thermally unstable, rendering the use of such materials hazardous because of the possibility of run-away decomposition.

The present invention is based on the discovery that radiation sensitive aromatic onium salts of Group VIa elements, such as ##STR1## can be incorporated in epoxy resins to provide one package radiation curable compositions which do not require a stabilizer to minimize cure at ambient temperatures during the shelf period, and are free of all of the aforementioned disadvantages of the aromatic diazonium salt compositions.

Included by the aromatic Group VIa onium salts which can be used to make the curable compositions of the invention are compounds of the formula, ##STR2## where R is a monovalent aromatic organic radical, R1 is a monovalent organic aliphatic radical selected from alkyl, cycloalkyl and substituted alkyl, R2 is a polyvalent organic radical forming a heterocyclic or fused ring structure selected from aliphatic radicals and aromatic radicals, X is a Group VIa element selected from sulfur, selenium and tellurium, M is a metal or metalloid, Q is a halogen radical, a is a whole number equal to 0 to 3 inclusive, b is a whole number equal to 0 to 2 inclusive, c is a whole number equal to 0 or 1, where the sum of a + b + c is a value equal to 3 or the valence of X,

d = e - f

f = valence of M and is an integer equal to from 2 to 7 inclusive

e is >f and is an integer having a value up to 8.

Radicals included by R are, for example, C.sub.(6-13) aromatic hydrocarbon radicals such as phenyl, tolyl, napthyl, anthryl, and such radicals substituted with up to 1 to 4 monovalent radicals such as C.sub.(1-8) alkoxy, C.sub.(1-8) alkyl, nitro, chloro, hydroxy, etc.; arylacyl radicals such as benzyl, phenylacyl, etc.; aromatic heterocyclic radicals such as pyridyl, furfuryl, etc. R1 radicals include C.sub.(1-8) alkyl, such as methyl, ethyl, etc., substituted alkyl such as -C2 H4 OCH3, -CH2 COOC2 H5, -CH2 COCH3, etc. R2 radicals include such structures as: ##STR3## Complex anions included by MQe -(e-f) of formula I are, for example, BF4 -, PF6 -, AsF6 -, SbF6 -, FeCl4 -, SnCl6 -, SbCl6 -, BiCl5 =, AlF6 -3, GaCl4 -, InF4 -, TiF6 =, ZrF6 -, etc., where M is a transition metal such as Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, Sc, V, Cr, Mn, Cs, rare earth elements such as the lanthanides, for example, Ce, Pr, Nd, etc., actinides, such as Th, Pa, U, Np, etc. and metalloids such as B, P, As, etc.

Group VIa onium salts included by Formula I are, for example, ##STR4##

There is provided by the present invention curable epoxy compositions comprising,

A. an epoxy resin polymerizable to a higher molecular weight state selected from epoxy monomer, epoxy prepolymer, oxirane containing organic polymer and mixtures thereof, and

B. an effective amount of a radiation sensitive aromatic Group VIa onium salt capable of effecting the cure of (A) by release of a Lewis Acid catalyst when exposed to radiant energy.

Group VIa onium salts of formula I are well known and can be made by the procedure shown in J. W. Knapczyk and W. E. McEwen, J. Am. Chem. Soc., 91 145, (1969); A. L. Maycock and G. A. Berchtold, J. Org. Chem. 35, No. 8, 2532 (1970); H. M. Pitt, U.S. Pat. No. 2,807,648, E. Goethals and P. De Radzetzky, Bul. Soc. Chim. Bleg., 73 546 (1964); H. M. Leicester and F. W. Bergstrom, J. Am. Chem. Soc., 51 3587 (1929), etc.

The term "epoxy resin" as utilized in the description of the curable compositions of the present invention, includes any monomeric, dimeric or oligomeric or polymeric epoxy material containing one or a plurality of epoxy functional groups. For example, those resins which result from the reaction of bisphenol-A (4,4'-isopropylidenediphenol) and epichlorohydrin, or by the reaction of low molecular weight phenol-formaldehyde resins (Novolak resins) with epichlorohydrin, can be used alone or in combination with an epoxy containing compound as a reactive diluent. Such diluents as phenyl glycidyl ether, 4-vinylcyclohexene dioxide, limonene dioxide, 1,2-cyclohexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide, allyl glycidyl ether, etc., may be added as viscosity modifying agents.

In addition, the range of these compounds can be extended to include polymeric materials containing terminal or pendant epoxy groups. Examples of these compounds are vinyl copolymers containing glycidyl acrylate or methacrylate as one of the comonomers. Other classes of epoxy containing polymers amenable to cure using the above catalysts are epoxy-siloxane resins, epoxy-polyurethanes and epoxy-polyesters. Such polymers usually have epoxy functional groups at the ends of their chains. Epoxy-siloxane resins and method for making are more particularly shown by E. P. Plueddemann and G. Fanger, J. Am. Chem. Soc. 81 632-5 (1959). As described in the literature, epoxy resins can also be modified in a number of standard ways such as reactions with amines, carboxylic acids, thiols, phenols, alcohols, etc. as shown in U.S. Pat. Nos. 2,935,488; 3,235,620; 3,369,055; 3,379,653; 3,398,211; 3,403,199; 3,563,850; 3,567,797; 3,677,995; etc. Further examples of epoxy resins which can be used are shown in the Encyclopedia of Polymer Science and Technology, Vol. 6, 1967, Interscience Publishers, New York, pp 209-271.

The curable compositions of the present invention can be made by blending the epoxy resin, which hereinafter will signify epoxy monomer, epoxy prepolymer, epoxy polymer or mixture thereof, with an effective amount of the Group VIa onium salt or "onium salt". The resulting curable composition which can be in the form of a varnish having a viscosity of from 1 centipoise to 100,000 centipoises at 25° C or a free flowing powder, can be applied to a variety of substrates by conventional means and cured to the tack-free state within 1 second or less to 10 minutes or more.

Depending upon the compatability of the onium salt with the epoxy resin, the Group VIa onium salt can be dissolved or dispersed therein along with an organic solvent such as nitromethane, acetonitrile, etc., prior to its incorporation. In instances where the epoxy resin is a solid, incorporation of the onium salt can be achieved by dry milling or by melt mixing the resin whereby the onium salt is incorporated.

It has been found that the onium salt also can be generated in situ in the presence of the epoxy resin if desired. For example, an onium salt of the formula,

(R).sub.a (R.sup.1).sub.b (R.sup.2).sub.c X.sup.+ Q'.sup.-,

where R, R1, R2, X, a, b and c are as previously defined, and Q'- is an anion such as Cl-, Br-, I-, F-, HSO4 -, NO3 -, etc., can be separately or simultaneously introduced into the epoxy resin with a Lewis Acid salt of the formula

M'[MQ]

where M' is a metal cation, such as Na+, K+, Ca++, Mg++, Fe++, Ni++, Co++, Zn++, etc. and organic cations such as ammonium, pyridinium, etc., and where [MQ] is defined in formula I above.

Experience has shown that the proportion of onium salt to epoxy resin can vary widely inasmuch as the salt is substantially inert, unless activated. Effective results can be achieved if a proportion of from 0.1% to 15% by weight of onium salt is employed, based on the weight of curable composition.

The curable compositions may contain inactive ingredients such as inorganic fillers, dyes, pigments, extenders, viscosity control agents, process aids, UV-screens, etc. in amounts of --0-- to 100 parts of filler per 100 parts of epoxy resin. The curable compositions can be applied to such substrates as metal, rubber, plastic, molded parts or films, paper, wood, glass cloth, concrete, ceramic, etc.

Some of the applications in which the curable compositions of the present invention can be used are, for example, protective, decorative and insulating coatings, potting compounds, printing inks, sealants, adhesives, photoresists, wire insulation, textile coatings, laminates, impregnated tapes, printing plates, etc.

Cure of the curable composition can be achieved by activating the onium salt to provide the release of the Lewis Acid catalyst. Activation of the onium salt can be achieved by heating the composition at a temperature in the range of from 150° C to 250° C. Preferably cure can be achieved by exposing the curable composition to radiant energy such as electron beam or ultraviolet light. Electron beam cure can be effected at an accelerator voltage of from about 100 to 1,000 KV. Cure of the compositions is preferably achieved by the use of UV irradiation having a wavelength of from 1849 A to 4000 A and an intensity of at least 5,000-80,000 microwatts per cm2. The lamp systems used to generate such radiation can consist of ultraviolet lamps such as from 1 to 50 discharge lamps, for example, xenon, metallic halide, metallic arc, such as a low, medium or high pressure mercury vapor discharge lamp, etc. having an operating pressure of from a few millimeters to about 10 atmospheres, etc., can be employed. The lamps can include envelopes capable of transmitting light of a wavelength of from about 1849 A to 4000 A, and preferably 2400 A to 4000 A. The lamp envelope can consist of quartz, such as Spectrocil, or Pyrex, etc. Typical lamps which can be employed for providing ultraviolet radiation are, for example, medium pressure mercury arcs, such as the GE H3T7 arc and the Hanovia 450 W arc lamp. The cures may be carried out with a combination of various lamps, some or all of which can operate in an inert atmosphere. When using UV lamps, the irradiation flux on the substrate can be at least 0.01 watts per square inch to effect cure of the organic resin within 1 to 20 seconds and permit the cure to be carried on continuously as, for example, in the curing of epoxy-coated steel strip to be taken up at a rate of from 100 to 600 feet per minute. The strip can be cut to a predetermined width for use as transformer laminates, etc. A combination of heat and light may be used to cure reactive compositions. Such a combination of heat and light may serve to reduce the overall cure time.

In order that those skilled in the art will be better able to practice the invention, the following examples are given by way of illustration and not by way of limitation. All parts are by weight.

EXAMPLE 1

A curable composition was prepared by forming a mixture of 0.2 part of triphenylsulfonium tetrafluoroborate dissolved in acetonitrile and 5 parts of 4-vinylcyclohexene dioxide. A 2 mil film was drawn on a glass plate and exposed to ultraviolet irradiation from a GE H3T7 lamp at a distance of from 6 inches. The resin had cured to a hard film within 30 seconds. The film was found to be insoluble in dipolar aprotic solvents and it could not be scratched with a fingernail.

A portion of the above curable composition having a viscosity at 25° C of about 6 centipoises was allowed to stand under average daylight conditions for 4 months in a transparent container. It was found that the viscosity remained substantially the same.

A portion of the curable composition was applied onto a steel strip. The treated steel surface was exposed 15 seconds to the ultraviolet radiation of an H3T7 lamp at a distance of 2 inches. A clear, tack-free film was formed which showed no signs of bubbles or other imperfections.

The above treated strip was then immersed in 10C hydrocarbon oil for 48 hours at 120° C to determine its hydrolytic stability in accordance with IFT test ASTM D971-50 Interfacial Tension of Oil Against Water shown on page 322 of the 1970 Annual Book of ASTM Standards, part 17 (November). The initial reading of the oil was about 39.0 dynes/cm. After the test the oil showed an interfacial tension reading of 38. In order to pass, a reading of at least 30 is required.

EXAMPLE 2

An 80:20 mixture of an epoxy novolak resin, an epoxy equivalent weight of 173 and 4-vinylcyclohexene dioxide was sensitized with 3% by weight of triphenylsulfonium hexafluoroantimonate. This solution was used to impregnate glass cloth. Two 6 in × 6 in squares of the cloth were then stacked together and cured to form a laminate by irradiating the cloth for 1 minute on each side using a GE H3T7 lamp at a distance of 6 inches. The stiff laminate was integrally bonded and could be used for circuit boards.

EXAMPLE 3

Triphenylselenonium chloride was prepared according to the procedure of H. M. Leicester and F. W. Bergstrom, J. Am. Chem. Soc., 51 3587 (1929) starting with diphenyl selenide. The corresponding fluoroborate, hexafluoroarsenate and hexafluoroantimonate salts were prepared by adding sodium hexafluoroarsenate, sodium tetrafluoroborate or potassium hexafluoroantimonate to an aqueous solution of triphenylselenonium chloride. The products were white crystalline solids which were dried in vacuo.

Three percent solutions of the above salts in 4-vinylcyclohexene dioxide were cured as 2 mil films at a distance of six inches from a GE H3T7 lamp. The following cure times were observed:

______________________________________Salt                  Cure Time______________________________________(C.sub.6 H.sub.5).sub.3 Se.sup.+ BF.sub.4.sup.-                 10 sec.(C.sub.6 H.sub.5).sub.3 Se.sup.+ AsF.sub.6.sup.-                  5 sec.(C.sub.6 H.sub.5).sub.3 Se.sup.+ SbF.sub.6.sup.-                  3 sec.______________________________________
EXAMPLE 4

There were added three parts phenacyl tetramethylene sulfonium hexafluoroarsenate to a 70:30 mixture of bisphenol-A-diglycidyl ether and 4-vinylcyclohexene dioxide. The catalyzed mixture of epoxides was then used to impregnate a 1 inch wide glass fabric tape. After winding one layer onto a 5 inches × 2 inches diameter cylinder, the impregnated tape was cured while rotating the wound cylinder under a GE H3T7 lamp. The total exposure time to UV light was 5 minutes. At the end of this time the tape was fully cured into the shape of a rigid cylinder. The wound cylinder could then be used as a spool for winding wire to make transformer coils.

EXAMPLE 5

A mixture was prepared consisting of 14.5 g (0.25 mole) glycidyl allyl ether, 10 mg t-butylcatechol, and three drops of chloroplatinic acid in octyl alcohol. The reaction mixture was heated to 50° C in a water bath and then 13.0 g of a polydimethyl siloxane resin containing 0.89% by weight Si-H groups was added dropwise by means of a dropping funnel. Immediate exothermic reaction took place with the temperature rising to 65° C. Reaction proceeded smoothly at this temperature giving a clear fluid resin.

Three parts by weight of triphenylsulfonium fluoroborate dissolved in a small amount of acetonitrile was added to 97 parts of the above silicone epoxy resin. A 2 mil film of the sensitized resin was drawn on a glass plate and then exposed to UV light from a GE H3T7 lamp at a distance of six inches. The film was tack-free within 15 to 20 seconds. A small amount of silica was added to the sensitized resin to produce a thixotropic mixture and the resin cured as described previously. A tough, rubbery coating resulted. These UV cured epoxy-siloxanes are useful as sealants and caulks.

EXAMPLE 6

There were added 3 parts S-phenyldibenzothiophenium fluoroborate to 97 parts 4-vinylcyclohexene dioxide. This mixture was spread on a glass plate as a 2 mil film and exposed to irradiaton from a GE H3T7 lamp at a distance of six inches. One minute exposure was required to fully cure the film to a hard, scratch resistant state.

EXAMPLE 7

A 3% solution of phenacyl tetramethylene sulfonium hexafluoroarsenate in 40:60 mixture of 4-vinylcyclohexene dioxide and an epoxy novolak having an epoxy equivalent weight of 206 were knife coated onto a steel plate to a thickness of 3 mil. A mask was placed over the film and the entire assembly irradiated for 1 minute. The mask was removed and the film was washed with i-propanol. The unexposed portions of the film were washed away having a clear sharp negative image of the mask.

EXAMPLE 8

There were added 6 parts of a 50% aqueous solution of triphenylsulfonium chloride and 2.1 parts of NaAsF6 to 97 parts of an 80:20 mixture of bisphenol-A-diglycidyl ether and 4-vinylcyclohexene dioxide. The reaction mixture was agitated by stirring for 1/2 hour and then allowed to settle. An aliquot of the resin was taken and spread onto a glass plate using a draw knife with a 3 ml aperture. A tack-free film formed within 15 seconds after exposure to an H3T7 lamp at a distance of 6 inches. The film was hard and clear.

Resistors were potted in the above resin by dipping the resistor into the sensitized resin and then curing it by rotating the resistor for 30 seconds beneath the ultraviolet lamp.

EXAMPLE 9

An equimolar mixture of diphenyliodonium fluoroborate and thioxanthene was heated at 200° C for 3 hours. After recrystallization from methylene chloride-diethyl ether, there was obtained an 80% yield of product having a m.p. of 168°-169° C. Based on method of preparation the product was S-phenylthioxanthene fluoroborate. A hard clear scratch resistant 1 mil coating was obtained, when a 3% solution of the above onium compound in limonene dioxide was knife coated onto a polystyrene sheet and exposed to UV irradiation from a 450 W Hanovia medium pressure mercury arc at a distance of 3 inches.

EXAMPLE 10

There were added 2.6 parts phenacyltetramethylene sulfonium bromide to a mixture of 95 parts of 4-vinylcyclohexene dioxide containing 2.2 parts of NaAsF6. The solution was placed in a dark bottle and rolled on a ball mill for 8 hours. After the salts were removed by filtration, the solution was coated onto a 3 in × 6 in steel panel and cured as in Example 1. A hard coating was obtained after 15 seconds exposure which could not be removed by rubbing the coating with acetone.

EXAMPLE 11

There were dissolved two parts of triphenylsulfonium hexafluoroantimonate into a 40:60 mixture of dicyclopentadiene dioxide and glycidyl acrylate. Following the procedure of example 1, a hard crosslinked 1 mil coating was obtained after a 15 second exposure to ultraviolet light.

EXAMPLE 12

There were added four parts of triphenylsulfonium hexafluoroarsenate to 100 parts of a blend of equal parts of 4-vinylcyclohexene dioxide and (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexanecarboxylate. An aliquot of the resulting sensitized resin was spread onto a polycarbonate sheet using a draw-down blade to give a 0.5 mil film. The film was cured as described in Example 1 for 10 seconds resulting in a clear hard mar resistant and solvent resistant coating.

EXAMPLE 13

A mixture of 50 parts bisphenol-A-diglycidyl ether and 50 parts (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexanecarboxylate was stirred until homogeneous. There was then added 3 parts of triphenylsulfonium hexafluoroantimonate to the solution. It was mixed until the sensitizer had dissolved. A portion of the above solution was coated onto a steel plate using a 0.2 mil drawbar. The plate was then exposed to a GE H3T7 lamp at a distance of 6 inches for 5 seconds. A hard cured adherent film formed on the steel.

EXAMPLE 14

A blend of epoxy resins consisting of 50 parts 4-vinylcyclohexene dioxide, 40 parts of a novolak-epoxy resin having an epoxy equivalent weight of 172-178 and 10 parts n-octylglycidyl ether were thoroughly mixed together. A 100 part aliquot was removed to which was added 1 part of triphenylsulfonium hexafluoroarsenate. The resulting mixture was stirred until the onium salt had dissolved. When the above mixture was coated onto a 3 in × 6 in steel panel and exposed to a 450 watt medium pressure mercury arc lamp at a distance of 3 inches, a glossy, dry coating was obtained in 2 seconds. The coating withstood attack by hot boiling water for 4 hours. It could not be removed by rubbing with acetone.

EXAMPLE 15

There was added 10 parts of a solid multifunctional aromatic glycidyl ether having an epoxy equivalent weight of 210-240 to 40 parts of limonene dioxide. The mixture was combined with 1 part of phenacyltetramethylene sulfonium hexafluoroarsenate and stirred at 50° C for 0.5 hour to produce a homogeneous solution. When the mixture was coated onto glass using a 0.5 mil drawbar, and irradiated for 5 seconds at a distance of 3 inches from a GE H3T7 mercury arc lamp having an intensity of 200 watts/sq. inch., a hard cured film was produced.

EXAMPLE 16

There was added 0.2 part of triphenylsulfonium hexafluoroantimonate in 2 parts of 4-vinylcyclohexene dioxide to 10 parts of an epoxidized butadiene resin. After mixing the components thoroughly, the mixture was applied to a 1/16 inch thick glass plate to a 1 mil thickness. Another plate of glass was placed on top of the first and the assembly was exposed to a GE H3T7 medium pressure mercury arc lamp having an intensity of 200 watts/sq. inch at a distance of three inches. The total exposure time was 30 seconds. The glass plates were permanently bonded together. Based on characteristics of the glass laminate, a similar procedure can be used to make a shatterproof windshield for automobiles.

EXAMPLE 17

There were added with stirring 89 parts of aluminum chloride in small portions to a solution of 122 parts of 2,6-xylenol in 505.12 parts of carbon disulfide maintained at 10° C. To the resulting greenish solution were added 79.5 parts of thionyl chloride in a dropwise fashion maintaining the temperature between 10° and 15° C. A black precipitate and solution was obtained which was stirred for an additional 2 hours and then poured onto 1,000 parts of ice containing about 50 parts of concentrated HCl. This mixture was placed on a steam bath to remove CS2 and to decompose the complex. A tan solid was obtained which was filtered, washed with water and dried.

To a solution of 21.5 parts of the above crude product in about 117 parts of hot absolute ethanol were added 11.4 parts of KAsF6 and 10 parts of water. The reaction mixture was stirred and more water was added to effect the precipitation of product. The product was filtered, washed with water and dried. A material was obtained having a m.p. of 245°-251° C. Based on method of preparation and elemental analysis for C24 H27 O3 SAsF6. Calc: % C, 49.3; % H, 4.62; % S, 5.48. Found: % C, 49.4; % H, 4.59; % S, 5.55, the product was tris-3,5-dimethyl-4-hydroxyphenyl sulfonium hexafluoroarsenate.

A 3 percent solution of the above onium salt was made with 4-vinylcyclohexene dioxide. Cure of the solution was effected by irradiating a 2 mil film on glass according to the procedure described in Example 3. A hard mar-resistant coating was obtained after 5 seconds of irradiation.

EXAMPLE 18

Three parts of triphenylsulfonium hexafluoroantimonate were ground to a fine powder. The powder was intimately mixed with 97 parts Reichhold Epotuf® 37-834 powder coating resin by tumbling these together for 30 minutes. The powder was then electrostatically sprayed onto 3 in × 6 in steel panels to form approximately a 2 mil coating using a GEMA model 171 spray gun. Subsequently, the samples were heated briefly to 150° C to fuse the powder and then exposed while hot to a GE H3T7 medium pressure mercury arc lamp at a distance of 3 inches. Cured samples were obtained after a 15 second irradiation. The cured films were adherent and mar resistant.

EXAMPLE 19

Triphenacyl hexafluoroarsenate was added to a mixture of 67% by weight of a novolak-epoxy resin having an epoxy equivalent weight of 172-178, 33% 4-vinylcyclohexene dioxide and 0.5% of a surface active agent. The resulting mixture contained about 1% by weight of the onium salt. A coating was applied as a 0.1 mil film to 3 in × 6 in steel plates and cured for 20 seconds at a distance of 4 inches from a GE H3T7 medium pressure mercury arc lamp. Some panels were subsequently immersed for 5 hours at room temperature in methylene chloride. Other panels were immersed for 4 hours in acetone. In all cases, no visible signs of solvent attack of the coatings were observed. The same were then baked for 1 hour at 160° C. Tests were run separately in boiling 50% KOH solution for 30 minutes and in boiling distilled water for 4 hours. Again, no visible degradation of the coatings was observed.

EXAMPLE 20

Mixtures of triphenylsulfonium hexafluoroarsenate in 4-vinylcyclohexene dioxide having a concentration of 0 to 10% onium salt, were thermally aged at 25° C and 55° C. The viscosities of the mixtures were measured over a 2-week period (336 hrs.). The following results were recorded at 25° C:

______________________________________          Viscosity    Viscosity atConcentration (%)          Start (cps)  336 hr (cps)______________________________________0              6.06         6.061              6.26         6.343              6.90         6.905              7.65         7.5910             9.80         9.71______________________________________

at 55° C:

______________________________________          Viscosity    Viscosity atConcentration (%)          Start (cps)  336 hr (cps)______________________________________0              6.06         6.061              6.42         6.373              6.91         6.935              7.65         7.6710             9.75         9.71______________________________________

Within experimental error, the above results show that there is essentially no viscosity change over the period the sensitizer was tested at a temperature range of 25° C to 55° C.

Although the above examples are limited to only a few of the very many curable compositions and uses thereof which are included within the scope of the present invention, it should be understood that the present invention is intended to cover a much broader class of curable compositions and uses thereof. Those skilled in the art would also know that the curable compositions also cover the use of onium polymers containing Group VIa onium functionality as part of the polymer backbone or in the pendant position.

Claims (15)

What I claim as new and desire to secure by letters patent of the United States is:
1. Photocurable compositions consisting essentially of
A. an epoxy resin polymerizable to a higher molecular weight state,
B. from 0.1 to 15% by weight of a photodecomposable aromatic onium salt of a Group VIa element capable of effecting the cure of epoxy resin when exposed to radiant energy wherein said aromatic onium salt has the formula
[(R).sub.a (R.sup.1).sub.b (R.sup.2).sub.c X].sub.d .sup.+ [MQ.sub.e ].sup.-(e-f)
where R is a monovalent aromatic organic radical, R1 is a monovalent organic aliphatic radical selected from alkyl, cycloalkyl and substituted alkyl, R2 is a polyvalent organic radical forming a heterocyclic or fused ring structure selected from aliphatic radicals and aromatic radicals, X is a Group VIa element selected from sulfur, selenium and tellurium, M is a metal or metalloid, Q is a halogen radical, a is a whole number equal to 0 to 3 inclusive, b is a whole number equal to 0 to 2 inclusive, c is a whole number equal to 0 or 1, where the sum of a + b + c is a value equal to 3 or the valence of X,
d = e - f
f = valence of M and is an integer equal to from 2 to 7 inclusive
e is >f and is an integer having a value up to 8 and
C. from 0 to 100 parts by weight of filler, per 100 parts of epoxy resin.
2. A photocurable composition in accordance with claim 1, where the onium salt is a sulfonium salt.
3. A photocurable composition in accordance with claim 1, where the onium salt is a selenium salt.
4. A photocurable composition in accordance with claim 1, where the onium salt is a tellurium salt.
5. A photocurable composition in accordance with claim 2, where the sulfonium salt is a dialkyl phenacyl sulfonium salt.
6. A photocurable composition in accordance with claim 1, having a sulfonium tetrafluoroborate salt.
7. A photocurable composition in accordance with claim 1, where the Group VIa onium salt is prepared in situ.
8. A composition in accordance with claim 1, where a mixture of onium salts are employed.
9. A composition in accordance with claim 1 in the form of a fluid at room temperature.
10. A photocurable composition in accordance with claim 1, in the form of a free-flowing powder.
11. A photocurable composition in accordance with claim 1, comprising a reaction product of 4,4'-isopropylidene diphenol and epichlorohydrin.
12. An article of manufacture comprising a substrate with a composition of claim 1.
13. A photocurable composition in accordance with claim 1, where the aromatic onium salt is triphenylsulfonium hexafluoroarsenate.
14. A photocurable composition in accordance with claim 1, where the aromatic onium salt is triphenylsulfonium hexafluoroantimonate.
15. A photocurable composition in accordance with claim 1, where the aromatic onium salt is triphenylsulfonium tetrafluoroborate.
US05638982 1974-05-02 1975-12-09 Photocurable compositions containing group via aromatic onium salts Expired - Lifetime US4058401A (en)

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US05840092 US4175972A (en) 1974-05-02 1977-10-06 Curable epoxy compositions containing aromatic onium salts and hydroxy compounds
US05861128 US4173551A (en) 1974-05-02 1977-12-16 Heat curable compositions

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Cited By (202)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4156046A (en) * 1977-03-28 1979-05-22 Minnesota Mining And Manufacturing Company Ultraviolet radiation protective, abrasion resistant, bloom resistant coatings
DE2904625A1 (en) * 1978-02-08 1979-08-09 Minnesota Mining & Mfg photopolymerizable mixtures
US4173476A (en) * 1978-02-08 1979-11-06 Minnesota Mining And Manufacturing Company Complex salt photoinitiator
US4173551A (en) * 1974-05-02 1979-11-06 General Electric Company Heat curable compositions
US4175972A (en) * 1974-05-02 1979-11-27 General Electric Company Curable epoxy compositions containing aromatic onium salts and hydroxy compounds
US4186108A (en) * 1978-02-08 1980-01-29 Minnesota Mining And Manufacturing Company Liquid compositions containing triarylsulfonium complex salts and oxyethylene material
US4197174A (en) * 1979-03-14 1980-04-08 American Can Company Method for producing bis-[4-(diphenylsulfonio) phenyl] sulfide bis-MX6
US4201640A (en) * 1979-03-14 1980-05-06 American Can Company Method for producing bis-[4-(diphenylsulfonio)phenyl] sulfide bis-M.X6
US4216288A (en) * 1978-09-08 1980-08-05 General Electric Company Heat curable cationically polymerizable compositions and method of curing same with onium salts and reducing agents
US4218279A (en) * 1977-07-05 1980-08-19 Ciba-Geigy Corporation Bonding method employing film adhesives containing an epoxide resin
WO1980001723A1 (en) * 1979-02-12 1980-08-21 Gen Electric Heat curable compositions
WO1980001695A1 (en) * 1979-02-12 1980-08-21 Gen Electric Curable organic resin compositions and foaming method
FR2451260A1 (en) * 1979-03-14 1980-10-10 American Can Co Method of coating substrates with epoxy resin
US4231886A (en) * 1979-01-29 1980-11-04 Minnesota Mining And Manufacturing Company Ester solutions of complex salts
US4238587A (en) * 1979-11-28 1980-12-09 General Electric Company Heat curable compositions
WO1980002838A1 (en) * 1979-06-14 1980-12-24 Gen Electric Heat curable compositions
FR2459265A1 (en) * 1979-06-18 1981-01-09 Gen Electric Stable mixture of arylsulfonium salt-solvent
US4245029A (en) * 1979-08-20 1981-01-13 General Electric Company Photocurable compositions using triarylsulfonium salts
DE3023696A1 (en) * 1979-06-29 1981-01-29 Gen Electric A polymerisable composition and the use thereof
WO1981000309A1 (en) * 1979-07-25 1981-02-05 Minnesota Mining & Mfg Pressure-sensitive adhesive susceptible to ultraviolet light-induced detackification
US4250006A (en) * 1979-03-19 1981-02-10 American Can Company Polymerizable coating composition containing polymerizable epoxide compound and vinyl chloride dispersion polymer and method of coating utilizing same and coated articles produced thereby
US4250053A (en) * 1979-05-21 1981-02-10 Minnesota Mining And Manufacturing Company Sensitized aromatic iodonium or aromatic sulfonium salt photoinitiator systems
US4250203A (en) * 1979-08-30 1981-02-10 American Can Company Cationically polymerizable compositions containing sulfonium salt photoinitiators and odor suppressants and method of polymerization using same
US4252592A (en) * 1977-07-05 1981-02-24 Ciba-Geigy Corporation Method of making epoxide resin-impregnated composites
US4256828A (en) * 1975-09-02 1981-03-17 Minnesota Mining And Manufacturing Company Photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials
US4259454A (en) * 1979-02-12 1981-03-31 General Electric Company Curable organic resin compositions and foaming method
JPS5667304A (en) * 1979-11-05 1981-06-06 American Can Co Cation polymerizable composition having stable free radical as sulfonium salt photoinitiator and deodorant and polymerization therefor
FR2472007A1 (en) * 1979-12-11 1981-06-26 Gen Electric Method for manufacturing composite articles bound by photopolymerization of epoxy resins sensitized with dyes
US4283312A (en) * 1977-12-16 1981-08-11 General Electric Company Heat curable processable epoxy compositions containing aromatic iodonium salt catalyst and copper salt cocatalyst
US4289595A (en) * 1979-11-26 1981-09-15 American Can Company Ambient temperature curing photopolymerizable epoxide compositions utilizing epoxide ethers and methods
FR2480762A1 (en) * 1980-04-21 1981-10-23 Gen Electric curable composition based UV of a-olefins oxides and for peelable adhesive coated paper such a composition
US4299938A (en) * 1979-06-19 1981-11-10 Ciba-Geigy Corporation Photopolymerizable and thermally polymerizable compositions
EP0044274A2 (en) * 1980-07-10 1982-01-20 Ciba-Geigy Ag Photopolymerisation by means of carbamoylsulfoxonium salts
US4318766A (en) * 1975-09-02 1982-03-09 Minnesota Mining And Manufacturing Company Process of using photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials
US4321404A (en) * 1980-05-20 1982-03-23 Minnesota Mining And Manufacturing Company Compositions for providing abherent coatings
US4324679A (en) * 1978-02-08 1982-04-13 Minnesota Mining And Manufacturing Company Controlling odor in photopolymerization
US4336363A (en) * 1979-02-12 1982-06-22 General Electric Company Heat curable compositions containing sulfonium salts
US4337303A (en) * 1980-08-11 1982-06-29 Minnesota Mining And Manufacturing Company Transfer, encapsulating, and fixing of toner images
US4339567A (en) * 1980-03-07 1982-07-13 Ciba-Geigy Corporation Photopolymerization by means of sulphoxonium salts
US4367251A (en) * 1980-04-21 1983-01-04 General Electric Company UV Curable compositions and substrates treated therewith
US4383878A (en) * 1980-05-20 1983-05-17 Minnesota Mining And Manufacturing Company Transfer process
EP0082603A2 (en) * 1981-12-22 1983-06-29 Mobil Oil Corporation Radiation curable epoxy/acrylate-hydroxyl coating compositions
US4398014A (en) * 1980-11-04 1983-08-09 Ciba-Geigy Corporation Sulfoxonium salts and their use as polymerization catalysts
EP0095269A2 (en) 1982-05-18 1983-11-30 Minnesota Mining And Manufacturing Company Radiation-sensitive compositions of polymers containing a pi-metal carbonyl complex of conjugated polyolefin
US4423136A (en) * 1977-08-05 1983-12-27 General Electric Company Free radical curable resin compositions containing triarylsulfonium salt
US4442197A (en) * 1982-01-11 1984-04-10 General Electric Company Photocurable compositions
US4500629A (en) * 1982-04-08 1985-02-19 Ciba-Geigy Corporation Method of forming images from liquid masses
US4511701A (en) * 1984-02-27 1985-04-16 General Electric Company Heat curable epoxy resin compositions and epoxy resin curing agents
EP0153904A2 (en) * 1984-02-10 1985-09-04 Ciba-Geigy Ag Process for the preparation of a protection layer or a relief pattern
US4572890A (en) * 1983-05-11 1986-02-25 Ciba-Geigy Corporation Process for the production of images
US4604344A (en) * 1984-02-03 1986-08-05 Ciba-Geigy Corporation Process for the production of images using sequentially liquid polymerizing compositions and photocuring
US4634644A (en) * 1983-12-20 1987-01-06 Ciba-Geigy Corporation Process for the production images using sequentially gaseous polymerizing agents and photocuring
US4654379A (en) * 1985-12-05 1987-03-31 Allied Corporation Semi-interpenetrating polymer networks
US4661429A (en) * 1986-04-28 1987-04-28 Eastman Kodak Company Photoelectrographic elements and imaging method
US4694029A (en) * 1985-04-09 1987-09-15 Cook Paint And Varnish Company Hybrid photocure system
EP0243159A2 (en) * 1986-04-22 1987-10-28 Minnesota Mining And Manufacturing Company Photopolymerizable compositions
US4708925A (en) * 1984-12-11 1987-11-24 Minnesota Mining And Manufacturing Company Photosolubilizable compositions containing novolac phenolic resin
US4725653A (en) * 1983-10-27 1988-02-16 Union Carbide Corporation Low viscosity adducts of a polycaprolactone polyol and a polyepoxide
EP0285369A2 (en) * 1987-04-02 1988-10-05 Minnesota Mining And Manufacturing Company Coated abrasive binder containing ternary photoinitiator system
US4818776A (en) * 1983-02-07 1989-04-04 Union Carbide Corporation Photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials having primary hydroxyl content
US4849320A (en) * 1986-05-10 1989-07-18 Ciba-Geigy Corporation Method of forming images
US4857437A (en) * 1986-12-17 1989-08-15 Ciba-Geigy Corporation Process for the formation of an image
US4892894A (en) * 1985-11-07 1990-01-09 Union Carbide Chemical And Plastics Company Inc. Photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials
US4933377A (en) * 1988-02-29 1990-06-12 Saeva Franklin D Novel sulfonium salts and the use thereof as photoinitiators
US4940651A (en) * 1988-12-30 1990-07-10 International Business Machines Corporation Method for patterning cationic curable photoresist
US4966922A (en) * 1988-06-09 1990-10-30 General Electric Company Dual curable silicone compositions
US4975300A (en) * 1987-12-31 1990-12-04 Minnesota Mining And Manufacturing Company Method for curing an organic coating using condensation heating and radiation energy
US4985473A (en) * 1980-05-20 1991-01-15 Minnesota Mining And Manufacturing Company Compositions for providing abherent coatings
US4997717A (en) * 1987-03-27 1991-03-05 Ciba-Geigy Corporation Photocurable abrasives
US5026624A (en) * 1989-03-03 1991-06-25 International Business Machines Corporation Composition for photo imaging
US5047568A (en) * 1988-11-18 1991-09-10 International Business Machines Corporation Sulfonium salts and use and preparation thereof
US5057550A (en) * 1989-12-04 1991-10-15 Dow Corning Corporation Epoxy-silanol functional uv curable polymers
US5077083A (en) * 1989-12-04 1991-12-31 Dow Corning Corporation Epoxy-silanol functional UV curable polymers
US5089374A (en) * 1990-08-20 1992-02-18 Eastman Kodak Company Novel bis-onium salts and the use thereof as photoinitiators
US5108859A (en) * 1990-04-16 1992-04-28 Eastman Kodak Company Photoelectrographic elements and imaging method
US5159088A (en) * 1989-07-22 1992-10-27 Basf Aktiengesellschaft Sulfonium salts and use thereof
US5166125A (en) * 1992-02-19 1992-11-24 Eastman Kodak Company Method of forming color filter array element with patternable overcoat layer
US5166126A (en) * 1992-02-19 1992-11-24 Eastman Kodak Company Color filter array element with protective overcoat layer and method of forming same
US5194365A (en) * 1985-06-19 1993-03-16 Ciba-Geigy Corporation Method for forming images
EP0541107A1 (en) * 1991-11-06 1993-05-12 Bridgestone Corporation Ultraviolet light curable adhesive active finish for reinforcing members and related methods
US5220037A (en) * 1989-07-22 1993-06-15 Basf Aktiengesellschaft Sulfonium salts and use thereof
US5238747A (en) * 1989-12-29 1993-08-24 The Dow Chemical Company Photocurable compositions
US5242715A (en) * 1991-02-18 1993-09-07 Siemens Aktiengesellschaft Process for coating or bonding electronic components and subassemblies
US5262232A (en) * 1992-01-22 1993-11-16 Minnesota Mining And Manufacturing Company Vibration damping constructions using acrylate-containing damping materials
US5264325A (en) * 1988-12-30 1993-11-23 International Business Machines Corporation Composition for photo imaging
US5274148A (en) * 1992-08-10 1993-12-28 Isp Investments, Inc. Dialky alkoxy phenyl sulfonium salt cationic initiators
US5278010A (en) * 1989-03-03 1994-01-11 International Business Machines Corporation Composition for photo imaging
US5296567A (en) * 1991-04-08 1994-03-22 Ciba-Geigy Corporation Thermocurable compositions
US5302438A (en) * 1989-12-05 1994-04-12 Konica Corporation Photographic-image-bearing recording member and method of its preparation
US5304457A (en) * 1989-03-03 1994-04-19 International Business Machines Corporation Composition for photo imaging
US5310619A (en) * 1986-06-13 1994-05-10 Microsi, Inc. Resist compositions comprising a phenolic resin, an acid forming onium salt and a tert-butyl ester or tert-butyl carbonate which is acid-cleavable
US5310581A (en) * 1989-12-29 1994-05-10 The Dow Chemical Company Photocurable compositions
US5322832A (en) * 1991-10-03 1994-06-21 Konica Corporation Image-receiving sheet for thermal-transfer recording medium
US5359017A (en) * 1990-11-16 1994-10-25 Nippon Kayaku Kabushiki Kaisha Cationically polymerizable organic material compositions and method for the stabilization thereof
US5362607A (en) * 1986-06-13 1994-11-08 Microsi, Inc. Method for making a patterned resist substrate composite
US5374697A (en) * 1992-07-21 1994-12-20 Ciba-Geigy Corporation Selected novel sulfonium compounds particularly suitable as initiators for the thermal cure of cationically polymerisable materials
US5374501A (en) * 1992-08-17 1994-12-20 Minnesota Mining And Manufacturing Company Alkali soluble photopolymer in color proofing constructions
US5399596A (en) * 1988-03-03 1995-03-21 Sanshin Kagaku Kogyo Co., Ltd. Polyfluoride sulfonium compounds and polymerization initiator thereof
US5439766A (en) * 1988-12-30 1995-08-08 International Business Machines Corporation Composition for photo imaging
US5439779A (en) * 1993-02-22 1995-08-08 International Business Machines Corporation Aqueous soldermask
US5447797A (en) * 1992-08-10 1995-09-05 Siemens Aktiengesellschaft Reaction resin mixture comprising epoxy resin, benzylthiolanium salt and sensitizer
US5460918A (en) * 1994-10-11 1995-10-24 Minnesota Mining And Manufacturing Company Thermal transfer donor and receptor with silicated surface for lithographic printing applications
US5464538A (en) * 1989-12-29 1995-11-07 The Dow Chemical Company Reverse osmosis membrane
US5474876A (en) * 1992-05-29 1995-12-12 Basf Lacke + Farben Ag Radiation-crosslinkable mixtures containing carboxyl-containing polymeric precursors
US5486545A (en) * 1992-12-09 1996-01-23 Rensselaer Polytechnic Institute Process for making propenyl ethers and photopolymerizable compositions containing them
US5487927A (en) * 1992-01-24 1996-01-30 Revlon Consumer Products Corporation Decorating method and products
US5500453A (en) * 1992-02-07 1996-03-19 Toyo Ink Manufacturing Co., Ltd. (Oxo)sulfonium complex, polymerizable composition containing the complex, and method of polymerizing the composition
US5512122A (en) * 1991-10-17 1996-04-30 Luminart Inc. Printing method
US5514728A (en) * 1993-07-23 1996-05-07 Minnesota Mining And Manufacturing Company Catalysts and initiators for polymerization
US5525736A (en) * 1991-11-06 1996-06-11 Ciba-Geigy Corporation Process for the production of cyclic sulfonium salts
US5525400A (en) * 1989-05-16 1996-06-11 Ciba-Geigy Corporation Information carrier and process for the production thereof
US5571359A (en) * 1992-01-24 1996-11-05 Revlon Consumer Products Corporation Radiation curable pigmented compositions
US5612445A (en) * 1995-02-15 1997-03-18 Arizona Chemical Co. Ultraviolet curable epoxidized alkyds
US5650262A (en) * 1992-10-29 1997-07-22 Muenzel; Norbert High-resolution negative photoresist with wide process latitude
WO1998014485A1 (en) * 1996-10-01 1998-04-09 Aeroplas Corporation International Electron-beam curable epoxy compositions
US5747223A (en) * 1988-12-30 1998-05-05 International Business Machines Corporation Composition for photoimaging
US5773528A (en) * 1990-10-31 1998-06-30 International Business Machines Corporation Dual cure epoxy backseal formulation
EP0851295A1 (en) * 1996-12-27 1998-07-01 Ecole Polytechnique Federale De Lausanne Process for the fabrication of microstructures by multilayer conformation of a photosensitive resin et microstructures obtained therewith
US5776634A (en) * 1990-11-22 1998-07-07 Canon Kabushiki Kaisha Photosensitive recording medium and method of preparing volume type phase hologram member using same
WO1999033906A1 (en) 1997-12-29 1999-07-08 Revlon Consumer Products Corporation Method and compositions for decorating vitreous articles with radiation curable inks having improved adhesion and durability
US5935661A (en) * 1994-09-06 1999-08-10 Herberts Powder Coatings, Inc. Radiation curing of powder coatings on heat sensitive substrates: chemical compositions and processes for obtaining coated workpieces
US5962547A (en) * 1997-05-16 1999-10-05 Nikolic; Nikola A. Reactive radiation- or thermally-initiated cationically-curable epoxide monomers and compositions made from those monomers
US6057382A (en) * 1998-05-01 2000-05-02 3M Innovative Properties Company Epoxy/thermoplastic photocurable adhesive composition
US6066889A (en) * 1998-09-22 2000-05-23 International Business Machines Corporation Methods of selectively filling apertures
US6077601A (en) * 1998-05-01 2000-06-20 3M Innovative Properties Company Coated abrasive article
US6093493A (en) * 1997-07-03 2000-07-25 Ciba Specialty Chemicals Corp. Method for the coating or encapsulation of fluidizable substrates
US6127490A (en) * 1997-08-26 2000-10-03 Ranbar Electrical Materials, Inc. Varnish compositions, methods of making and components made therefrom
US6129955A (en) * 1995-10-26 2000-10-10 International Business Machines Corporation Encapsulating a solder joint with a photo cured epoxy resin or cyanate
US6136398A (en) * 1998-05-01 2000-10-24 3M Innovative Properties Company Energy cured sealant composition
US6180317B1 (en) 1988-12-30 2001-01-30 International Business Machines Corporation Composition for photoimaging
US6204456B1 (en) 1998-09-24 2001-03-20 International Business Machines Corporation Filling open through holes in a multilayer board
US6210862B1 (en) 1989-03-03 2001-04-03 International Business Machines Corporation Composition for photoimaging
US6228133B1 (en) 1998-05-01 2001-05-08 3M Innovative Properties Company Abrasive articles having abrasive layer bond system derived from solid, dry-coated binder precursor particles having a fusible, radiation curable component
US6235358B1 (en) * 1997-02-20 2001-05-22 Toyo Seikan Kaisha, Ltd. Package container and container closure
US6254954B1 (en) 1997-02-28 2001-07-03 3M Innovative Properties Company Pressure-sensitive adhesive tape
US6274643B1 (en) 1998-05-01 2001-08-14 3M Innovative Properties Company Epoxy/thermoplastic photocurable adhesive composition
US6310850B1 (en) 1999-07-29 2001-10-30 Siros Technologies, Inc. Method and apparatus for optical data storage and/or retrieval by selective alteration of a holographic storage medium
US6322933B1 (en) 1999-01-12 2001-11-27 Siros Technologies, Inc. Volumetric track definition for data storage media used to record data by selective alteration of a format hologram
US6322931B1 (en) 1999-07-29 2001-11-27 Siros Technologies, Inc. Method and apparatus for optical data storage using non-linear heating by excited state absorption for the alteration of pre-formatted holographic gratings
WO2002000561A2 (en) 2000-06-29 2002-01-03 Essilor International Compagnie Generale D'optique Process for making an abrasion resistant coating onto an organic glass substrate
US6387486B1 (en) 1999-10-29 2002-05-14 Adhesives Research, Inc. Pressure sensitive adhesive tape and silicone-free release coating used therein
US6488993B2 (en) 1997-07-02 2002-12-03 William V Madigan Process for applying a coating to sheet metal
US20020189476A1 (en) * 2001-03-06 2002-12-19 Keitaro Aoshima Planographic printing plate precursor
US6512606B1 (en) 1999-07-29 2003-01-28 Siros Technologies, Inc. Optical storage media and method for optical data storage via local changes in reflectivity of a format grating
DE3702999C2 (en) * 1987-02-02 2003-03-06 Siemens Ag Apparatus for processing UV-curable reaction resin compositions and their uses
US20030094738A1 (en) * 2001-09-28 2003-05-22 Brother Kogyo Kabushiki Kaisha Active energy beam-curable composition, ink containing the same, and printer accommodating the same ink
US6599954B1 (en) * 1997-10-17 2003-07-29 Mitsubishi Heavy Industries, Ltd. Resin curing method enabling the energy radiation curing of resins containing an energy radiation screening substance, compositions, molded articles and molded methods
US20030158286A1 (en) * 2002-01-28 2003-08-21 Brother Kogyo Kabushiki Kaisha Active energy beam-curable composition
US6627762B1 (en) 2002-10-23 2003-09-30 John G. Woods Acetal and hemiacetal ester linked propylene carbonate functional (meth)acrylic esters and method of making same
US20030218269A1 (en) * 2001-09-28 2003-11-27 Brother Kogyo Kabushiki Kaisha Image-receiving layer composition and overcoat layer composition for ink-jet recording
WO2004009720A2 (en) 2002-07-24 2004-01-29 Adhesives Research, Inc. Transformable pressure sensitive adhesive tape and use thereof in display screens
US6737204B2 (en) 2001-09-04 2004-05-18 Kodak Polychrome Graphics, Llc Hybrid proofing method
US20040106769A1 (en) * 2000-07-11 2004-06-03 Hatton Kevin Brian High functional polymers
US6764616B1 (en) 1999-11-29 2004-07-20 Huntsman Advanced Materials Americas Inc. Hydrophobic epoxide resin system
US20050020710A1 (en) * 2001-11-06 2005-01-27 Masami Ishihara Hybrid onium salt
US6855748B1 (en) 1999-09-16 2005-02-15 Huntsman Advanced Materials Americas, Inc. UV-curable compositions
US20050096405A1 (en) * 2001-07-10 2005-05-05 Deco Patents, Inc. UV cured UV blocking compositions and methods for making and using the same
US20050189834A1 (en) * 2004-02-27 2005-09-01 Hitachi, Ltd. Rotating machines, insulation coils, and epoxy resin composition for rotating machines and insulation coils
US20050233253A1 (en) * 2002-03-04 2005-10-20 Wako Pure Chemical Industries, Ltd Heterocycle-bearing onium salts
WO2006032492A1 (en) 2004-09-23 2006-03-30 Securis Limited High speed manufacture of microstructures
US20070021523A1 (en) * 2005-07-25 2007-01-25 Treadway Gerald D Optical coating composition
US7199192B2 (en) 2004-12-21 2007-04-03 Callaway Golf Company Golf ball
US20070272607A1 (en) * 2006-05-24 2007-11-29 Millipore Corporation Membrane surface modification by radiation-induced polymerization
US20090030106A1 (en) * 2007-07-23 2009-01-29 Henkel Corporation Photosensitive Compounds, Photopolymerizable Compositions Including the Same, and Methods of Making and Using the Same
WO2009083488A1 (en) 2007-12-31 2009-07-09 Nivarox-Far S.A. Method for obtaining a metal microstructure and microstructure obtained according to said method
EP2157476A1 (en) 2008-08-20 2010-02-24 Nivarox-FAR S.A. Method of manufacturing multi-level metal parts using the LIGA-UV technique
EP2182096A1 (en) 2008-10-28 2010-05-05 Nivarox-FAR S.A. Heterogeneous LIGA method
US7714037B1 (en) 2006-12-15 2010-05-11 Henkel Corporation Photoinitiated cationic epoxy compositions and articles exhibiting low color
EP2236488A1 (en) 2001-03-30 2010-10-06 The Arizona Board of Regents on behalf of the University of Arizona Materials, methods and uses for photochemical generation of acids and/or radical species
EP2263972A1 (en) 2009-06-12 2010-12-22 Nivarox-FAR S.A. Method for manufacturing a metal microstructure and microstructure obtained according to this method
US20110008733A1 (en) * 2008-03-11 2011-01-13 3M Innovative Properties Company Phototools having a protective layer
US20110065045A1 (en) * 2009-09-16 2011-03-17 Zai-Ming Qiu Epoxy-functionalized perfluoropolyether polyurethanes
US8030401B1 (en) 2006-08-03 2011-10-04 Henkel Corporation Photoinitiated cationic epoxy compositions
WO2011134686A1 (en) 2010-04-29 2011-11-03 Huntsman Advanced Materials (Switzerland) Gmbh Curable composition
WO2012009120A2 (en) 2010-06-28 2012-01-19 Dow Global Technologies Llc Curable resin compositions
WO2012009118A2 (en) 2010-06-28 2012-01-19 Dow Global Technologies Llc Curable resin compositions
EP2497647A1 (en) 2011-02-15 2012-09-12 Bergstein B.V. Process for decorating glazed ceramic tiles
WO2013057265A1 (en) 2011-10-21 2013-04-25 Tesa Se Adhesive substance, in particular for encapsulating an electronic assembly
WO2013059286A1 (en) 2011-10-19 2013-04-25 3M Innovative Properties Company Hardcoat compositions
DE102012206273A1 (en) 2012-04-17 2013-10-17 Tesa Se Linkable adhesive with hard and soft blocks as Permeantenbarriere
WO2013188070A1 (en) 2012-06-15 2013-12-19 Dow Global Technologies Llc Curable compositions
DE102012222056A1 (en) 2012-12-03 2014-06-05 Tesa Se Lamination of rigid substrates with thin adhesive tapes
US8748060B2 (en) 2009-09-16 2014-06-10 3M Innovative Properties Company Fluorinated coating and phototools made therewith
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US9011983B2 (en) 2011-07-29 2015-04-21 Ideon Llc Process for curing a composition by electron beam radiation, and by gas-generated plasma and ultraviolet radiation
US9051423B2 (en) 2009-09-16 2015-06-09 3M Innovative Properties Company Fluorinated coating and phototools made therewith
US9096712B2 (en) 2009-07-21 2015-08-04 3M Innovative Properties Company Curable compositions, method of coating a phototool, and coated phototool
WO2016066437A1 (en) 2014-10-29 2016-05-06 Tesa Se Adhesive compounds comprising multi-functional siloxane water scavengers
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US9465288B2 (en) 2012-12-07 2016-10-11 Dsp Gokyo Food & Chemical Co., Ltd. Sulfonium salt compound, method for producing the same, and photoacid generator
EP3091059A1 (en) 2015-05-05 2016-11-09 tesa SE Adhesive tape with adhesive mass with continuous polymer phase
DE102015217860A1 (en) 2015-05-05 2016-11-10 Tesa Se Tape with adhesive, with a continuous polymer phase
EP3101079A1 (en) 2015-06-04 2016-12-07 tesa SE Steam blocking adhesive with anpolymerised epoxide syrup
EP3101047A1 (en) 2015-06-04 2016-12-07 tesa SE Method for producing viscous epoxide syrups and epoxide syrups obtainable therefrom
WO2016202608A1 (en) 2015-06-16 2016-12-22 Huntsman Advanced Materials (Switzerland) Gmbh Epoxy resin composition
WO2017001182A1 (en) 2015-07-02 2017-01-05 Huntsman Advanced Materials (Switzerland) Gmbh A thermosetting epoxy resin composition for the preparation of outdoor articles, and the articles obtained therefrom
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DE102016207550A1 (en) 2016-05-02 2017-11-02 Tesa Se Functionalized (co) polymers for adhesive systems and adhesive tapes
DE102016207540A1 (en) 2016-05-02 2017-11-02 Tesa Se Water vapor barrier adhesive with hochfunktionalisiertem poly (meth) acrylate
US9856394B2 (en) 2015-03-19 2018-01-02 Mark Alan Litman Dye-tintable, abrasion resistant coating for ophthalmic lenses and method of application

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3373221A (en) * 1964-11-04 1968-03-12 Shell Oil Co Reaction products of unsaturated esters of polyepoxides and unsaturated carboxylic acids, and polyisocyanates
US3412046A (en) * 1965-07-01 1968-11-19 Dexter Corp Catalyzed polyepoxide-anhydride resin systems
US3567453A (en) * 1967-12-26 1971-03-02 Eastman Kodak Co Light sensitive compositions for photoresists and lithography
US3729313A (en) * 1971-12-06 1973-04-24 Minnesota Mining & Mfg Novel photosensitive systems comprising diaryliodonium compounds and their use
US3816280A (en) * 1971-05-18 1974-06-11 American Can Co Photopolymerizable epoxy systems containing cyclic amide gelation inhibitors
US3816281A (en) * 1973-04-30 1974-06-11 American Can Co Poly(vinyl pyrrolidone)stabilized polymerized epoxy compositions and process for irradiating same
US3826650A (en) * 1968-08-20 1974-07-30 American Can Co Epoxy photopolymer duplicating stencil

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3373221A (en) * 1964-11-04 1968-03-12 Shell Oil Co Reaction products of unsaturated esters of polyepoxides and unsaturated carboxylic acids, and polyisocyanates
US3412046A (en) * 1965-07-01 1968-11-19 Dexter Corp Catalyzed polyepoxide-anhydride resin systems
US3567453A (en) * 1967-12-26 1971-03-02 Eastman Kodak Co Light sensitive compositions for photoresists and lithography
US3826650A (en) * 1968-08-20 1974-07-30 American Can Co Epoxy photopolymer duplicating stencil
US3816280A (en) * 1971-05-18 1974-06-11 American Can Co Photopolymerizable epoxy systems containing cyclic amide gelation inhibitors
US3729313A (en) * 1971-12-06 1973-04-24 Minnesota Mining & Mfg Novel photosensitive systems comprising diaryliodonium compounds and their use
US3816281A (en) * 1973-04-30 1974-06-11 American Can Co Poly(vinyl pyrrolidone)stabilized polymerized epoxy compositions and process for irradiating same

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Banks, Chemical Review, vol. 66, No. 3, (1966), pp. 243-263. *
Fieser et al., Org. Chem. 3rd Ed., Reinhold, pp. 140-141. *
Irving et al., J. Chem. Soc. (1960), pp. 2078-2081. *
Knapczyk et al., J. Org. Chem., vol. 35, No. 8, (1970), pp. 2539-2543. *
Kunieda et al., Polymer Letters Edition, vol. 12, pp. 395-397, 7/1974. *

Cited By (271)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4173551A (en) * 1974-05-02 1979-11-06 General Electric Company Heat curable compositions
US4175972A (en) * 1974-05-02 1979-11-27 General Electric Company Curable epoxy compositions containing aromatic onium salts and hydroxy compounds
US4256828A (en) * 1975-09-02 1981-03-17 Minnesota Mining And Manufacturing Company Photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials
US4318766A (en) * 1975-09-02 1982-03-09 Minnesota Mining And Manufacturing Company Process of using photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials
US4156046A (en) * 1977-03-28 1979-05-22 Minnesota Mining And Manufacturing Company Ultraviolet radiation protective, abrasion resistant, bloom resistant coatings
US4252592A (en) * 1977-07-05 1981-02-24 Ciba-Geigy Corporation Method of making epoxide resin-impregnated composites
US4218279A (en) * 1977-07-05 1980-08-19 Ciba-Geigy Corporation Bonding method employing film adhesives containing an epoxide resin
US4423136A (en) * 1977-08-05 1983-12-27 General Electric Company Free radical curable resin compositions containing triarylsulfonium salt
US4283312A (en) * 1977-12-16 1981-08-11 General Electric Company Heat curable processable epoxy compositions containing aromatic iodonium salt catalyst and copper salt cocatalyst
DE2904625A1 (en) * 1978-02-08 1979-08-09 Minnesota Mining & Mfg photopolymerizable mixtures
US4173476A (en) * 1978-02-08 1979-11-06 Minnesota Mining And Manufacturing Company Complex salt photoinitiator
US4218531A (en) * 1978-02-08 1980-08-19 Minnesota Mining And Manufacturing Company Addition of ethylenically unsaturated materials to control odor in photopolymerizable epoxy compositions
US4324679A (en) * 1978-02-08 1982-04-13 Minnesota Mining And Manufacturing Company Controlling odor in photopolymerization
US4186108A (en) * 1978-02-08 1980-01-29 Minnesota Mining And Manufacturing Company Liquid compositions containing triarylsulfonium complex salts and oxyethylene material
US4216288A (en) * 1978-09-08 1980-08-05 General Electric Company Heat curable cationically polymerizable compositions and method of curing same with onium salts and reducing agents
US4231886A (en) * 1979-01-29 1980-11-04 Minnesota Mining And Manufacturing Company Ester solutions of complex salts
WO1980001723A1 (en) * 1979-02-12 1980-08-21 Gen Electric Heat curable compositions
US4241204A (en) * 1979-02-12 1980-12-23 General Electric Company Cationically curable organic resin compositions containing sulfonium salts and an organic oxidant
US4336363A (en) * 1979-02-12 1982-06-22 General Electric Company Heat curable compositions containing sulfonium salts
WO1980001695A1 (en) * 1979-02-12 1980-08-21 Gen Electric Curable organic resin compositions and foaming method
US4230814A (en) * 1979-02-12 1980-10-28 General Electric Company Heat curable compositions
US4259454A (en) * 1979-02-12 1981-03-31 General Electric Company Curable organic resin compositions and foaming method
US4197174A (en) * 1979-03-14 1980-04-08 American Can Company Method for producing bis-[4-(diphenylsulfonio) phenyl] sulfide bis-MX6
FR2451260A1 (en) * 1979-03-14 1980-10-10 American Can Co Method of coating substrates with epoxy resin
US4201640A (en) * 1979-03-14 1980-05-06 American Can Company Method for producing bis-[4-(diphenylsulfonio)phenyl] sulfide bis-M.X6
US4250006A (en) * 1979-03-19 1981-02-10 American Can Company Polymerizable coating composition containing polymerizable epoxide compound and vinyl chloride dispersion polymer and method of coating utilizing same and coated articles produced thereby
US4250053A (en) * 1979-05-21 1981-02-10 Minnesota Mining And Manufacturing Company Sensitized aromatic iodonium or aromatic sulfonium salt photoinitiator systems
WO1980002838A1 (en) * 1979-06-14 1980-12-24 Gen Electric Heat curable compositions
FR2459265A1 (en) * 1979-06-18 1981-01-09 Gen Electric Stable mixture of arylsulfonium salt-solvent
US4299938A (en) * 1979-06-19 1981-11-10 Ciba-Geigy Corporation Photopolymerizable and thermally polymerizable compositions
DE3023696A1 (en) * 1979-06-29 1981-01-29 Gen Electric A polymerisable composition and the use thereof
US4308118A (en) * 1979-06-29 1981-12-29 General Electric Company Deep section curable epoxy resin putty
JPS56500889A (en) * 1979-07-25 1981-07-02
US4286047A (en) * 1979-07-25 1981-08-25 Minnesota Mining And Manufacturing Company Pressure-sensitive adhesive susceptible to ultraviolet light-induced detackification
WO1981000309A1 (en) * 1979-07-25 1981-02-05 Minnesota Mining & Mfg Pressure-sensitive adhesive susceptible to ultraviolet light-induced detackification
US4245029A (en) * 1979-08-20 1981-01-13 General Electric Company Photocurable compositions using triarylsulfonium salts
JPH0316361B2 (en) * 1979-08-30 1991-03-05 Asahi Denka Kogyo Kk
US4250203A (en) * 1979-08-30 1981-02-10 American Can Company Cationically polymerizable compositions containing sulfonium salt photoinitiators and odor suppressants and method of polymerization using same
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US4306953A (en) * 1979-11-05 1981-12-22 American Can Company Cationically polymerizable compositions containing sulfonium salt photoinitiators and stable free radicals as odor suppressants and _method of polymerization using same
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JPS5667304A (en) * 1979-11-05 1981-06-06 American Can Co Cation polymerizable composition having stable free radical as sulfonium salt photoinitiator and deodorant and polymerization therefor
US4289595A (en) * 1979-11-26 1981-09-15 American Can Company Ambient temperature curing photopolymerizable epoxide compositions utilizing epoxide ethers and methods
US4238587A (en) * 1979-11-28 1980-12-09 General Electric Company Heat curable compositions
FR2472007A1 (en) * 1979-12-11 1981-06-26 Gen Electric Method for manufacturing composite articles bound by photopolymerization of epoxy resins sensitized with dyes
US4356050A (en) * 1979-12-11 1982-10-26 General Electric Company Method of adhesive bonding using visible light cured epoxies
US4339567A (en) * 1980-03-07 1982-07-13 Ciba-Geigy Corporation Photopolymerization by means of sulphoxonium salts
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US4367251A (en) * 1980-04-21 1983-01-04 General Electric Company UV Curable compositions and substrates treated therewith
US4319974A (en) * 1980-04-21 1982-03-16 General Electric Company UV Curable compositions and substrates treated therewith
US4985473A (en) * 1980-05-20 1991-01-15 Minnesota Mining And Manufacturing Company Compositions for providing abherent coatings
US4383878A (en) * 1980-05-20 1983-05-17 Minnesota Mining And Manufacturing Company Transfer process
US4321404A (en) * 1980-05-20 1982-03-23 Minnesota Mining And Manufacturing Company Compositions for providing abherent coatings
US4383025A (en) * 1980-07-10 1983-05-10 Ciba-Geigy Corporation Photopolymerization by means of sulfoxonium salts
EP0044274A2 (en) * 1980-07-10 1982-01-20 Ciba-Geigy Ag Photopolymerisation by means of carbamoylsulfoxonium salts
EP0044274A3 (en) * 1980-07-10 1983-01-26 Ciba-Geigy Ag Photopolymerisation by means of carbamoylsulfoxonium salts
US4337303A (en) * 1980-08-11 1982-06-29 Minnesota Mining And Manufacturing Company Transfer, encapsulating, and fixing of toner images
US4398014A (en) * 1980-11-04 1983-08-09 Ciba-Geigy Corporation Sulfoxonium salts and their use as polymerization catalysts
EP0082603A2 (en) * 1981-12-22 1983-06-29 Mobil Oil Corporation Radiation curable epoxy/acrylate-hydroxyl coating compositions
EP0082603A3 (en) * 1981-12-22 1985-01-23 Mobil Oil Corporation Radiation curable epoxy/acrylate-hydroxyl coating compositions
US4442197A (en) * 1982-01-11 1984-04-10 General Electric Company Photocurable compositions
US4500629A (en) * 1982-04-08 1985-02-19 Ciba-Geigy Corporation Method of forming images from liquid masses
EP0095269A2 (en) 1982-05-18 1983-11-30 Minnesota Mining And Manufacturing Company Radiation-sensitive compositions of polymers containing a pi-metal carbonyl complex of conjugated polyolefin
US4818776A (en) * 1983-02-07 1989-04-04 Union Carbide Corporation Photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials having primary hydroxyl content
US4572890A (en) * 1983-05-11 1986-02-25 Ciba-Geigy Corporation Process for the production of images
US4725653A (en) * 1983-10-27 1988-02-16 Union Carbide Corporation Low viscosity adducts of a polycaprolactone polyol and a polyepoxide
US4634644A (en) * 1983-12-20 1987-01-06 Ciba-Geigy Corporation Process for the production images using sequentially gaseous polymerizing agents and photocuring
US4604344A (en) * 1984-02-03 1986-08-05 Ciba-Geigy Corporation Process for the production of images using sequentially liquid polymerizing compositions and photocuring
EP0153904A3 (en) * 1984-02-10 1987-03-25 Ciba-Geigy Ag Process for the preparation of a protection layer or a relief pattern
EP0153904A2 (en) * 1984-02-10 1985-09-04 Ciba-Geigy Ag Process for the preparation of a protection layer or a relief pattern
US4511701A (en) * 1984-02-27 1985-04-16 General Electric Company Heat curable epoxy resin compositions and epoxy resin curing agents
US4708925A (en) * 1984-12-11 1987-11-24 Minnesota Mining And Manufacturing Company Photosolubilizable compositions containing novolac phenolic resin
US4694029A (en) * 1985-04-09 1987-09-15 Cook Paint And Varnish Company Hybrid photocure system
US5194365A (en) * 1985-06-19 1993-03-16 Ciba-Geigy Corporation Method for forming images
US4892894A (en) * 1985-11-07 1990-01-09 Union Carbide Chemical And Plastics Company Inc. Photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials
US4654379A (en) * 1985-12-05 1987-03-31 Allied Corporation Semi-interpenetrating polymer networks
EP0243159A2 (en) * 1986-04-22 1987-10-28 Minnesota Mining And Manufacturing Company Photopolymerizable compositions
EP0243159A3 (en) * 1986-04-22 1988-11-30 Minnesota Mining And Manufacturing Company Photopolymerizable compositions
US4661429A (en) * 1986-04-28 1987-04-28 Eastman Kodak Company Photoelectrographic elements and imaging method
US4849320A (en) * 1986-05-10 1989-07-18 Ciba-Geigy Corporation Method of forming images
US5310619A (en) * 1986-06-13 1994-05-10 Microsi, Inc. Resist compositions comprising a phenolic resin, an acid forming onium salt and a tert-butyl ester or tert-butyl carbonate which is acid-cleavable
US5362607A (en) * 1986-06-13 1994-11-08 Microsi, Inc. Method for making a patterned resist substrate composite
US4857437A (en) * 1986-12-17 1989-08-15 Ciba-Geigy Corporation Process for the formation of an image
DE3702999C2 (en) * 1987-02-02 2003-03-06 Siemens Ag Apparatus for processing UV-curable reaction resin compositions and their uses
US4997717A (en) * 1987-03-27 1991-03-05 Ciba-Geigy Corporation Photocurable abrasives
EP0285369A2 (en) * 1987-04-02 1988-10-05 Minnesota Mining And Manufacturing Company Coated abrasive binder containing ternary photoinitiator system
EP0285369A3 (en) * 1987-04-02 1990-12-05 Minnesota Mining And Manufacturing Company Coated abrasive binder containing ternary photoinitiator system
US4975300A (en) * 1987-12-31 1990-12-04 Minnesota Mining And Manufacturing Company Method for curing an organic coating using condensation heating and radiation energy
US5470994A (en) * 1988-02-29 1995-11-28 Eastman Kodak Company Sulfonium salts and the use thereof as photoinitiators
US4933377A (en) * 1988-02-29 1990-06-12 Saeva Franklin D Novel sulfonium salts and the use thereof as photoinitiators
US5399596A (en) * 1988-03-03 1995-03-21 Sanshin Kagaku Kogyo Co., Ltd. Polyfluoride sulfonium compounds and polymerization initiator thereof
US4966922A (en) * 1988-06-09 1990-10-30 General Electric Company Dual curable silicone compositions
US5047568A (en) * 1988-11-18 1991-09-10 International Business Machines Corporation Sulfonium salts and use and preparation thereof
US4940651A (en) * 1988-12-30 1990-07-10 International Business Machines Corporation Method for patterning cationic curable photoresist
US6180317B1 (en) 1988-12-30 2001-01-30 International Business Machines Corporation Composition for photoimaging
US5264325A (en) * 1988-12-30 1993-11-23 International Business Machines Corporation Composition for photo imaging
US5747223A (en) * 1988-12-30 1998-05-05 International Business Machines Corporation Composition for photoimaging
US5439766A (en) * 1988-12-30 1995-08-08 International Business Machines Corporation Composition for photo imaging
US5278010A (en) * 1989-03-03 1994-01-11 International Business Machines Corporation Composition for photo imaging
US6210862B1 (en) 1989-03-03 2001-04-03 International Business Machines Corporation Composition for photoimaging
US5304457A (en) * 1989-03-03 1994-04-19 International Business Machines Corporation Composition for photo imaging
US5026624A (en) * 1989-03-03 1991-06-25 International Business Machines Corporation Composition for photo imaging
US5702557A (en) * 1989-05-16 1997-12-30 Ciba Specialty Chemicals Corporation Process for the production of an information carrier
US5525400A (en) * 1989-05-16 1996-06-11 Ciba-Geigy Corporation Information carrier and process for the production thereof
US5159088A (en) * 1989-07-22 1992-10-27 Basf Aktiengesellschaft Sulfonium salts and use thereof
US5220037A (en) * 1989-07-22 1993-06-15 Basf Aktiengesellschaft Sulfonium salts and use thereof
US5057550A (en) * 1989-12-04 1991-10-15 Dow Corning Corporation Epoxy-silanol functional uv curable polymers
US5077083A (en) * 1989-12-04 1991-12-31 Dow Corning Corporation Epoxy-silanol functional UV curable polymers
US5302438A (en) * 1989-12-05 1994-04-12 Konica Corporation Photographic-image-bearing recording member and method of its preparation
US5238747A (en) * 1989-12-29 1993-08-24 The Dow Chemical Company Photocurable compositions
US5310581A (en) * 1989-12-29 1994-05-10 The Dow Chemical Company Photocurable compositions
US5464538A (en) * 1989-12-29 1995-11-07 The Dow Chemical Company Reverse osmosis membrane
US5108859A (en) * 1990-04-16 1992-04-28 Eastman Kodak Company Photoelectrographic elements and imaging method
US5089374A (en) * 1990-08-20 1992-02-18 Eastman Kodak Company Novel bis-onium salts and the use thereof as photoinitiators
US5773528A (en) * 1990-10-31 1998-06-30 International Business Machines Corporation Dual cure epoxy backseal formulation
US5359017A (en) * 1990-11-16 1994-10-25 Nippon Kayaku Kabushiki Kaisha Cationically polymerizable organic material compositions and method for the stabilization thereof
US5776634A (en) * 1990-11-22 1998-07-07 Canon Kabushiki Kaisha Photosensitive recording medium and method of preparing volume type phase hologram member using same
US5242715A (en) * 1991-02-18 1993-09-07 Siemens Aktiengesellschaft Process for coating or bonding electronic components and subassemblies
US5296567A (en) * 1991-04-08 1994-03-22 Ciba-Geigy Corporation Thermocurable compositions
US5322832A (en) * 1991-10-03 1994-06-21 Konica Corporation Image-receiving sheet for thermal-transfer recording medium
US5512122A (en) * 1991-10-17 1996-04-30 Luminart Inc. Printing method
EP0541107A1 (en) * 1991-11-06 1993-05-12 Bridgestone Corporation Ultraviolet light curable adhesive active finish for reinforcing members and related methods
US5525736A (en) * 1991-11-06 1996-06-11 Ciba-Geigy Corporation Process for the production of cyclic sulfonium salts
US5262232A (en) * 1992-01-22 1993-11-16 Minnesota Mining And Manufacturing Company Vibration damping constructions using acrylate-containing damping materials
US5670006A (en) * 1992-01-22 1997-09-23 Minnesota Mining And Manufacturing Company Vibration damping constructions using acrylate-containing damping materials
US5571359A (en) * 1992-01-24 1996-11-05 Revlon Consumer Products Corporation Radiation curable pigmented compositions
US5487927A (en) * 1992-01-24 1996-01-30 Revlon Consumer Products Corporation Decorating method and products
US5500453A (en) * 1992-02-07 1996-03-19 Toyo Ink Manufacturing Co., Ltd. (Oxo)sulfonium complex, polymerizable composition containing the complex, and method of polymerizing the composition
US5166125A (en) * 1992-02-19 1992-11-24 Eastman Kodak Company Method of forming color filter array element with patternable overcoat layer
US5166126A (en) * 1992-02-19 1992-11-24 Eastman Kodak Company Color filter array element with protective overcoat layer and method of forming same
US5474876A (en) * 1992-05-29 1995-12-12 Basf Lacke + Farben Ag Radiation-crosslinkable mixtures containing carboxyl-containing polymeric precursors
US5374697A (en) * 1992-07-21 1994-12-20 Ciba-Geigy Corporation Selected novel sulfonium compounds particularly suitable as initiators for the thermal cure of cationically polymerisable materials
US5447797A (en) * 1992-08-10 1995-09-05 Siemens Aktiengesellschaft Reaction resin mixture comprising epoxy resin, benzylthiolanium salt and sensitizer
US5274148A (en) * 1992-08-10 1993-12-28 Isp Investments, Inc. Dialky alkoxy phenyl sulfonium salt cationic initiators
WO1994003551A1 (en) * 1992-08-10 1994-02-17 Isp Investments Inc. Dialkyl alkoxy phenyl sulfonium salt cationic initiators
US5374501A (en) * 1992-08-17 1994-12-20 Minnesota Mining And Manufacturing Company Alkali soluble photopolymer in color proofing constructions
US5650262A (en) * 1992-10-29 1997-07-22 Muenzel; Norbert High-resolution negative photoresist with wide process latitude
US5486545A (en) * 1992-12-09 1996-01-23 Rensselaer Polytechnic Institute Process for making propenyl ethers and photopolymerizable compositions containing them
US5567858A (en) * 1992-12-09 1996-10-22 Rensselaer Polytechnic Institute Propenyl ether monomers for photopolymerization
US5439779A (en) * 1993-02-22 1995-08-08 International Business Machines Corporation Aqueous soldermask
US5514728A (en) * 1993-07-23 1996-05-07 Minnesota Mining And Manufacturing Company Catalysts and initiators for polymerization
US5935661A (en) * 1994-09-06 1999-08-10 Herberts Powder Coatings, Inc. Radiation curing of powder coatings on heat sensitive substrates: chemical compositions and processes for obtaining coated workpieces
US5460918A (en) * 1994-10-11 1995-10-24 Minnesota Mining And Manufacturing Company Thermal transfer donor and receptor with silicated surface for lithographic printing applications
US5612445A (en) * 1995-02-15 1997-03-18 Arizona Chemical Co. Ultraviolet curable epoxidized alkyds
US5821324A (en) * 1995-02-15 1998-10-13 International Paper Company Ultraviolet curable epoxidized alkyds
US6129955A (en) * 1995-10-26 2000-10-10 International Business Machines Corporation Encapsulating a solder joint with a photo cured epoxy resin or cyanate
WO1998014485A1 (en) * 1996-10-01 1998-04-09 Aeroplas Corporation International Electron-beam curable epoxy compositions
FR2757961A1 (en) * 1996-12-27 1998-07-03 Ecole Polytech Microstructural METHOD multilayer conformation of a photosensitive resin and microstructures thus obtained
EP0851295A1 (en) * 1996-12-27 1998-07-01 Ecole Polytechnique Federale De Lausanne Process for the fabrication of microstructures by multilayer conformation of a photosensitive resin et microstructures obtained therewith
US6235358B1 (en) * 1997-02-20 2001-05-22 Toyo Seikan Kaisha, Ltd. Package container and container closure
US6254954B1 (en) 1997-02-28 2001-07-03 3M Innovative Properties Company Pressure-sensitive adhesive tape
US5962547A (en) * 1997-05-16 1999-10-05 Nikolic; Nikola A. Reactive radiation- or thermally-initiated cationically-curable epoxide monomers and compositions made from those monomers
US6488993B2 (en) 1997-07-02 2002-12-03 William V Madigan Process for applying a coating to sheet metal
US6093493A (en) * 1997-07-03 2000-07-25 Ciba Specialty Chemicals Corp. Method for the coating or encapsulation of fluidizable substrates
US6127490A (en) * 1997-08-26 2000-10-03 Ranbar Electrical Materials, Inc. Varnish compositions, methods of making and components made therefrom
US6599954B1 (en) * 1997-10-17 2003-07-29 Mitsubishi Heavy Industries, Ltd. Resin curing method enabling the energy radiation curing of resins containing an energy radiation screening substance, compositions, molded articles and molded methods
WO1999033906A1 (en) 1997-12-29 1999-07-08 Revlon Consumer Products Corporation Method and compositions for decorating vitreous articles with radiation curable inks having improved adhesion and durability
US6753359B2 (en) 1998-05-01 2004-06-22 3M Innovative Properties Company Abrasive articles having abrasive layer bond system derived from solid, dry-coated binder precursor particles having a fusible, radiation curable component
US6228133B1 (en) 1998-05-01 2001-05-08 3M Innovative Properties Company Abrasive articles having abrasive layer bond system derived from solid, dry-coated binder precursor particles having a fusible, radiation curable component
US6077601A (en) * 1998-05-01 2000-06-20 3M Innovative Properties Company Coated abrasive article
US6359027B1 (en) 1998-05-01 2002-03-19 3M Innovative Properties Company Coated abrasive article
US6258138B1 (en) 1998-05-01 2001-07-10 3M Innovative Properties Company Coated abrasive article
US6057382A (en) * 1998-05-01 2000-05-02 3M Innovative Properties Company Epoxy/thermoplastic photocurable adhesive composition
US6136398A (en) * 1998-05-01 2000-10-24 3M Innovative Properties Company Energy cured sealant composition
US6372336B1 (en) 1998-05-01 2002-04-16 3M Innovative Properties Company Coated abrasive article
US6136384A (en) * 1998-05-01 2000-10-24 3M Innovative Properties Company Epoxy/thermoplastic photocurable adhesive composition
US6441058B2 (en) 1998-05-01 2002-08-27 3M Innovative Properties Company Abrasive articles having abrasive layer bond system derived from solid, dry-coated binder precursor particles having a fusible, radiation curable component
US6274643B1 (en) 1998-05-01 2001-08-14 3M Innovative Properties Company Epoxy/thermoplastic photocurable adhesive composition
US20020123548A1 (en) * 1998-05-01 2002-09-05 3M Innovative Properties Company Abrasive articles having abrasive layer bond system derived from solid, dry-coated binder precursor particles having a fusible, radiation curable component
US6066889A (en) * 1998-09-22 2000-05-23 International Business Machines Corporation Methods of selectively filling apertures
US6376158B1 (en) 1998-09-22 2002-04-23 International Business Machines Corporation Methods for selectively filling apertures
US6204456B1 (en) 1998-09-24 2001-03-20 International Business Machines Corporation Filling open through holes in a multilayer board
US6322933B1 (en) 1999-01-12 2001-11-27 Siros Technologies, Inc. Volumetric track definition for data storage media used to record data by selective alteration of a format hologram
US6322931B1 (en) 1999-07-29 2001-11-27 Siros Technologies, Inc. Method and apparatus for optical data storage using non-linear heating by excited state absorption for the alteration of pre-formatted holographic gratings
US6512606B1 (en) 1999-07-29 2003-01-28 Siros Technologies, Inc. Optical storage media and method for optical data storage via local changes in reflectivity of a format grating
US6310850B1 (en) 1999-07-29 2001-10-30 Siros Technologies, Inc. Method and apparatus for optical data storage and/or retrieval by selective alteration of a holographic storage medium
DE20023994U1 (en) 1999-09-16 2008-12-18 Huntsman Advanced Materials (Switzerland) Gmbh UV-curable compositions
US7202286B2 (en) 1999-09-16 2007-04-10 Huntsman Advanced Materials Americas Inc. UV-curable compositions
US20050171228A1 (en) * 1999-09-16 2005-08-04 Hatton Kevin B. UV-curable compositions
US6855748B1 (en) 1999-09-16 2005-02-15 Huntsman Advanced Materials Americas, Inc. UV-curable compositions
US6387486B1 (en) 1999-10-29 2002-05-14 Adhesives Research, Inc. Pressure sensitive adhesive tape and silicone-free release coating used therein
US6764616B1 (en) 1999-11-29 2004-07-20 Huntsman Advanced Materials Americas Inc. Hydrophobic epoxide resin system
WO2002000561A2 (en) 2000-06-29 2002-01-03 Essilor International Compagnie Generale D'optique Process for making an abrasion resistant coating onto an organic glass substrate
US20040106769A1 (en) * 2000-07-11 2004-06-03 Hatton Kevin Brian High functional polymers
US20020189476A1 (en) * 2001-03-06 2002-12-19 Keitaro Aoshima Planographic printing plate precursor
US7074542B2 (en) * 2001-03-06 2006-07-11 Fuji Photo Film Co., Ltd. Planographic printing plate precursor
EP2236488A1 (en) 2001-03-30 2010-10-06 The Arizona Board of Regents on behalf of the University of Arizona Materials, methods and uses for photochemical generation of acids and/or radical species
US20050096405A1 (en) * 2001-07-10 2005-05-05 Deco Patents, Inc. UV cured UV blocking compositions and methods for making and using the same
US6737204B2 (en) 2001-09-04 2004-05-18 Kodak Polychrome Graphics, Llc Hybrid proofing method
US20030218269A1 (en) * 2001-09-28 2003-11-27 Brother Kogyo Kabushiki Kaisha Image-receiving layer composition and overcoat layer composition for ink-jet recording
US6866376B2 (en) 2001-09-28 2005-03-15 Brother Kogyo Kabushiki Kaisha Active energy beam-curable composition, ink containing the same, and printer accommodating the same ink
US20030094738A1 (en) * 2001-09-28 2003-05-22 Brother Kogyo Kabushiki Kaisha Active energy beam-curable composition, ink containing the same, and printer accommodating the same ink
US20050020710A1 (en) * 2001-11-06 2005-01-27 Masami Ishihara Hybrid onium salt
US7101918B2 (en) 2001-11-06 2006-09-05 Wako Pure Chemical Industries, Ltd. Hybrid type onium salt
US20030158286A1 (en) * 2002-01-28 2003-08-21 Brother Kogyo Kabushiki Kaisha Active energy beam-curable composition
US20050233253A1 (en) * 2002-03-04 2005-10-20 Wako Pure Chemical Industries, Ltd Heterocycle-bearing onium salts
US7833691B2 (en) 2002-03-04 2010-11-16 Wako Pure Chemical Industries, Ltd. Heterocycle-bearing onium salts
EP1953149A2 (en) 2002-03-04 2008-08-06 Wako Pure Chemical Industries, Ltd. A heterocycle-containing onium salt
US7318991B2 (en) 2002-03-04 2008-01-15 Wako Pure Chemical Industries, Ltd. Heterocycle-bearing onium salts
US20080161520A1 (en) * 2002-03-04 2008-07-03 Wako Pure Chemical Industries, Ltd. Heterocycle-bearing onium salts
WO2004009720A2 (en) 2002-07-24 2004-01-29 Adhesives Research, Inc. Transformable pressure sensitive adhesive tape and use thereof in display screens
US6627762B1 (en) 2002-10-23 2003-09-30 John G. Woods Acetal and hemiacetal ester linked propylene carbonate functional (meth)acrylic esters and method of making same
US20050189834A1 (en) * 2004-02-27 2005-09-01 Hitachi, Ltd. Rotating machines, insulation coils, and epoxy resin composition for rotating machines and insulation coils
WO2006032492A1 (en) 2004-09-23 2006-03-30 Securis Limited High speed manufacture of microstructures
US7199192B2 (en) 2004-12-21 2007-04-03 Callaway Golf Company Golf ball
US20070021523A1 (en) * 2005-07-25 2007-01-25 Treadway Gerald D Optical coating composition
US20080311408A1 (en) * 2005-07-25 2008-12-18 The Walman Optical Company Optical Coating Composition
US7514482B2 (en) 2005-07-25 2009-04-07 The Walman Optical Company Optical coating composition
US20100068539A1 (en) * 2005-07-25 2010-03-18 Treadway Gerald D Optical coating composition
US7717273B2 (en) 2006-05-24 2010-05-18 Millipore Corporation Membrane surface modification by radiation-induced polymerization
US20070272607A1 (en) * 2006-05-24 2007-11-29 Millipore Corporation Membrane surface modification by radiation-induced polymerization
EP2283914A1 (en) 2006-05-24 2011-02-16 Millipore Corporation Membrane surface modification by radiation-induced polymerization
US8030401B1 (en) 2006-08-03 2011-10-04 Henkel Corporation Photoinitiated cationic epoxy compositions
US7714037B1 (en) 2006-12-15 2010-05-11 Henkel Corporation Photoinitiated cationic epoxy compositions and articles exhibiting low color
US7705064B2 (en) 2007-07-23 2010-04-27 Henkel Corporation Photosensitive compounds, photopolymerizable compositions including the same, and methods of making and using the same
US20090030106A1 (en) * 2007-07-23 2009-01-29 Henkel Corporation Photosensitive Compounds, Photopolymerizable Compositions Including the Same, and Methods of Making and Using the Same
WO2009083488A1 (en) 2007-12-31 2009-07-09 Nivarox-Far S.A. Method for obtaining a metal microstructure and microstructure obtained according to said method
US8557506B2 (en) 2007-12-31 2013-10-15 Nivarox-Far S.A. Method of fabricating a metallic microstructure and microstructure obtained via the method
US20110020754A1 (en) * 2007-12-31 2011-01-27 Nivarox-Far S.A. Method of fabricating a metallic microstructure and microstructure obtained via the method
US20110008733A1 (en) * 2008-03-11 2011-01-13 3M Innovative Properties Company Phototools having a protective layer
US8663874B2 (en) 2008-03-11 2014-03-04 3M Innovative Properties Company Hardcoat composition
US20110027702A1 (en) * 2008-03-11 2011-02-03 3M Innovative Properties Company Hardcoat composition
EP2712900A1 (en) 2008-03-11 2014-04-02 3M Innovative Properties Company Phototools having a protective layer
US8563221B2 (en) 2008-03-11 2013-10-22 3M Innovative Properties Company Phototools having a protective layer
US20110146070A1 (en) * 2008-08-20 2011-06-23 Nivarox-Far S.A. Method of fabricating multi-level metallic parts by the liga-uv technique
EP2157476A1 (en) 2008-08-20 2010-02-24 Nivarox-FAR S.A. Method of manufacturing multi-level metal parts using the LIGA-UV technique
US9250533B2 (en) 2008-08-20 2016-02-02 Nivarox-Far S.A. Method of fabricating multi-level metallic parts by the liga-UV technique
WO2010049246A1 (en) 2008-10-28 2010-05-06 Nivarox-Far S.A. Heterogenous liga method
US20110203934A1 (en) * 2008-10-28 2011-08-25 Nivarox-Far S.A. Heterogeneous liga method
EP2182096A1 (en) 2008-10-28 2010-05-05 Nivarox-FAR S.A. Heterogeneous LIGA method
US8470154B2 (en) 2008-10-28 2013-06-25 Nivarox-Far S.A. Heterogeneous LIGA method
US9194052B2 (en) 2009-06-12 2015-11-24 Nivarox-Far S.A. Method of fabricating a plurality of metallic microstructures
EP2263972A1 (en) 2009-06-12 2010-12-22 Nivarox-FAR S.A. Method for manufacturing a metal microstructure and microstructure obtained according to this method
US9096712B2 (en) 2009-07-21 2015-08-04 3M Innovative Properties Company Curable compositions, method of coating a phototool, and coated phototool
US9051423B2 (en) 2009-09-16 2015-06-09 3M Innovative Properties Company Fluorinated coating and phototools made therewith
US8420281B2 (en) 2009-09-16 2013-04-16 3M Innovative Properties Company Epoxy-functionalized perfluoropolyether polyurethanes
US20110065045A1 (en) * 2009-09-16 2011-03-17 Zai-Ming Qiu Epoxy-functionalized perfluoropolyether polyurethanes
WO2011034885A2 (en) 2009-09-16 2011-03-24 3M Innovative Properties Company Epoxy-functionalized perfluoropolyether polyurethanes
US8748060B2 (en) 2009-09-16 2014-06-10 3M Innovative Properties Company Fluorinated coating and phototools made therewith
WO2011134686A1 (en) 2010-04-29 2011-11-03 Huntsman Advanced Materials (Switzerland) Gmbh Curable composition
WO2012009120A2 (en) 2010-06-28 2012-01-19 Dow Global Technologies Llc Curable resin compositions
WO2012009118A2 (en) 2010-06-28 2012-01-19 Dow Global Technologies Llc Curable resin compositions
US9695272B2 (en) 2010-06-28 2017-07-04 Blue Cube Ip Llc Divinylarene dioxide resin compositions
EP2497647A1 (en) 2011-02-15 2012-09-12 Bergstein B.V. Process for decorating glazed ceramic tiles
US9011983B2 (en) 2011-07-29 2015-04-21 Ideon Llc Process for curing a composition by electron beam radiation, and by gas-generated plasma and ultraviolet radiation
WO2013059286A1 (en) 2011-10-19 2013-04-25 3M Innovative Properties Company Hardcoat compositions
WO2013057265A1 (en) 2011-10-21 2013-04-25 Tesa Se Adhesive substance, in particular for encapsulating an electronic assembly
DE102012202377A1 (en) 2011-10-21 2013-04-25 Tesa Se Adhesive composition especially for encapsulating an electronic assembly
US9487684B2 (en) 2012-04-17 2016-11-08 Tesa Se Cross-linkable adhesive compound with hard and soft blocks as a permeant barrier
DE102012206273A1 (en) 2012-04-17 2013-10-17 Tesa Se Linkable adhesive with hard and soft blocks as Permeantenbarriere
WO2013188070A1 (en) 2012-06-15 2013-12-19 Dow Global Technologies Llc Curable compositions
DE102012222056A1 (en) 2012-12-03 2014-06-05 Tesa Se Lamination of rigid substrates with thin adhesive tapes
US9465288B2 (en) 2012-12-07 2016-10-11 Dsp Gokyo Food & Chemical Co., Ltd. Sulfonium salt compound, method for producing the same, and photoacid generator
WO2014117993A1 (en) 2013-01-29 2014-08-07 Tesa Se Pressure-sensitive adhesive compound containing a cross-linked nanoparticle network, method of production and use thereof
EP2759514A1 (en) 2013-01-29 2014-07-30 tesa SE Adhesive mass containing a connected nanoparticle network, process for its preparation and utilisation of the same
WO2016066437A1 (en) 2014-10-29 2016-05-06 Tesa Se Adhesive compounds comprising multi-functional siloxane water scavengers
WO2016108061A1 (en) 2014-12-30 2016-07-07 Essilor International (Compagnie Generale D'optique) Uv curable coating compositions for improved abrasion resistance
WO2016108060A1 (en) 2014-12-30 2016-07-07 Essilor International (Compagnie Generale D'optique) Compositions and methods for improving adhesion with a sputtered coating
US9856394B2 (en) 2015-03-19 2018-01-02 Mark Alan Litman Dye-tintable, abrasion resistant coating for ophthalmic lenses and method of application
DE102015217860A1 (en) 2015-05-05 2016-11-10 Tesa Se Tape with adhesive, with a continuous polymer phase
EP3091059A1 (en) 2015-05-05 2016-11-09 tesa SE Adhesive tape with adhesive mass with continuous polymer phase
DE102015210346A1 (en) 2015-06-04 2016-12-08 Tesa Se A process for the production of viscous Epoxidsirupe and thereafter available Epoxidsirupe
EP3101047A1 (en) 2015-06-04 2016-12-07 tesa SE Method for producing viscous epoxide syrups and epoxide syrups obtainable therefrom
EP3101079A1 (en) 2015-06-04 2016-12-07 tesa SE Steam blocking adhesive with anpolymerised epoxide syrup
DE102015210345A1 (en) 2015-06-04 2016-12-08 Tesa Se Water vapor barrier end adhesive with anpolymerisiertem Epoxidsirup
WO2016202608A1 (en) 2015-06-16 2016-12-22 Huntsman Advanced Materials (Switzerland) Gmbh Epoxy resin composition
WO2017001182A1 (en) 2015-07-02 2017-01-05 Huntsman Advanced Materials (Switzerland) Gmbh A thermosetting epoxy resin composition for the preparation of outdoor articles, and the articles obtained therefrom
WO2017083280A1 (en) 2015-11-11 2017-05-18 3M Innovative Properties Company Multilayer construction including barrier layer and sealing layer
WO2017174303A1 (en) 2016-04-04 2017-10-12 Tesa Se Radiation-activatable pressure-sensitive adhesive tape having a dark reaction and use thereof
DE102016207550A1 (en) 2016-05-02 2017-11-02 Tesa Se Functionalized (co) polymers for adhesive systems and adhesive tapes
DE102016207540A1 (en) 2016-05-02 2017-11-02 Tesa Se Water vapor barrier adhesive with hochfunktionalisiertem poly (meth) acrylate

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